Patent GB-775027-A (GB)
Title: Improvements in or relating to complex metal salt-soap compounds
IPC: C07C51/41
Filed: 1954-07-20
Abstract: Greases comprise silicones thickened with a complex of a metal salt of a C12-C30 carboxylic acid and a metal (other than aluminium) salt of an aliphatic carboxylic acid of lower molecular weight than the first, and containing more than 7, preferably 7-45, mols. of the latter salt for each mol. of the first.  The C12-C30, preferably C18-C22, acids include saturated and unsaturated fatty acids, e.g. stearic and hydroxy stearic; arachidic, hydrogenated fish oil, tallow, oleic and ricinoleic acids.  The lower molecular weight acids include saturated and unsaturated, mono- and poly-carboxylic C1-C6 acids, and hydroxy-acids, e.g. acetic, formic, propionic, acrylic, adipic, and lactic acids.  The metals include alkaline earths, particularly Ca, Ba and Mg, heavy metals of Groups 1, 2 and 4, especially Cu, Zn and Pb, either alone or with alkaline earths, and Ni, Co, Cr and Mn.  The complexes may be prepared by co-neutralization of the acid mixture in a medium in which the complex is to be used.  Heating to 450-550 DEG  F. or higher is generally effected to dehydrate and promote complex formation.  The acids may be replaced by such derivatives as esters or nitriles under conditions conducive to saponification. Alternatively, the metal salts may be separately preformed and then mixed and heated.  The complexes are compounded with silicones to form greases containing 5-30, and detergent or extreme pressure lubricants containing 0.5-20 weight per cent of complex.  In examples: (21) silicone fluid is thickened to a grease by mixing with acetic and Hydrofol (hydrogenated fish oil) acids and heating with lime; (22), (23) hydroxystearic acid and di-2-ethyl hexyl sebacate or di - iso - octyl azelate are also incorporated.ALSO:The invention comprises a complex of a metal (other than aluminium) salt of a C12-C30 carboxylic acid and a metal (other than aluminium) salt of an aliphatic carboxylic acid of lower molecular weight than the first, and containing more than 7, preferably 7-45, mols. of the latter salt for each mol. of the first.  The C12-330, preferably C18-C22, acids include saturated and unsaturated fatty acids, e.g. stearic and hydroxy stearic, arachidic, hydrogenated fish oil, tallow, oleic, and ricinoleic acids.  The lower molecular weight acids include saturated and unsaturated mono- and poly-carboxylic C1-C6 acids and hydroxy-acids, e.g. acetic, formic, propionic, acrylic, adipic, and lactic acids. The metals include alkaline earths, particularly Ca, Ba and Mg, heavy metals of Groups 1, 2, and 4, especially Cu, Zn, and Pb, either alone or with alkaline earths, and Ni, Co, Cr and Mn.  The complexes may be prepared by co-neutralization of the acid mixture with, for example, the metal hydroxide or carbonate, if desired in a lubricating oil or other medium in which the complex is to be used.  Heating to 450-550 DEG F. or higher is generally effected to dehydrate and promote complex formation.  The acids may be replaced by such derivatives as esters or nitriles under conditions conducive to saponification. Alternatively, the metal salts may be separately preformed and then mixed and heated.  When the complex is prepared in a liquid medium, it may be isolated by extraction with a solvent, e.g. heptane, isopropanol, acetone or water.  The complexes are compounded with mineral or synthetic oils, paints, and residual fuels.  The compositions may also include oil-soluble sulphonates equivalent to 25-80 weight per cent of the C12-C30 acid, and less than 5 per cent sulphurized sperm oil.  Cobalt complexes are of use as oxo catalysts and paint driers, nickel complexes as hydrogenation catalysts.  In examples: (1) greases are prepared by heating mineral oil, Hydrofol acid (hydrogenated fish oil acids), hydrogenated castor oil, and hydrated lime to 130 DEG F., adding various ratios of acetic acid, heating to 500 DEG F., cooling, and homogenizing; (2) the castor oil acid is omitted; (3) mono- and di-hydroxystearic acids are also incorporated to prevent hardening, and phenyl a -naphthylamine added during cooling; (6) and (7) cup greases are prepared by heating a calcium complex salt with a simple soap cup grease; (8) a grease containing equimolar amounts of Hydrofol acid and sulphonic acids as calcium salts is prepared; (9) a mixed sodium-calcium grease is obtained by mixing equal weights of the single metal complex greases; (10) a zinc-calcium grease is prepared by neutralizing the acids with zinc oxide and lime; (11) a softer grade is obtained by cutting back with more mineral oil, and the addition of titania is referred to; (12) greases are compared wherein the calcium acetate is wholly or partly preformed or prepared in situ; (13) the acetate content is part preformed strontium acetate and part calcium acetate made in situ; (14), (15) formic acid or a mixture with acetic is used; (16) lactic acid is the low molecular weight acid; (17) lead acetate is incorporated; (20) a twister ring lubricant comprises a calcium complex concentrate and petrolatum; (21) silicone fluid is thickened to a grease by mixing with acetic and Hydrofol acids and heating with lime; (22), (23) hydroxystearic acid and di-2-ethyl hexyl sebacate or di-iso-octyl azelate are also incorporated; (24) a polyester lubricating oil is used as medium for formation of the calcium complex; (25) calcium sulphonate is included in a calcium complex concentrate used as an additive for heavy duty lubricating oil. Specifications 659,103, 662,650 and 680,438 are referred to.ALSO:The invention comprises a complex of a metal (other than aluminium) salt of a C12-C30 carboxylic acid and a metal (other than aluminium) salt of an aliphatic carboxylic acid of lower molecular weight than the first, and containing more than 7, preferably 7-45, mols of the latter salt for each mol of the first.  The C12-C30, preferably C18-C22, acids include saturated and unsaturated fatty acids, e.g. stearic and hydroxy stearic, arachidic, hydrogenated fish oil, tallow, oleic and ricinoleic acids.  The lower molecular weight acids include saturated and unsaturated, mono- and polycarboxylic C1-C6 acids, and hydroxy-acids, e.g. acetic, formic, propionic, acrylic, adipic, and lactic acids.  The metals include alkaline earths, particularly Ca, Ba and Mg, heavy metals of Groups 1, 2 and 4, especially Cu, Zn and Pb, either alone or with alkaline earths, and Ni, Co, Cr and Mn.  The complexes may be prepared by co-neutralization of the acid mixture with, for example, the metal hydroxide or carbonate, if desired in a lubricating oil or other medium in which the complex is to be used.  Heating to 450-550 DEG F. or higher is generally effected to dehydrate and promote complex formation.  The acids may be replaced by such derivatives as esters or nitriles under conditions conducive to saponification. Alternatively, the metal salts may be separately preformed and then mixed and heated.  The complexes may be compounded with mineral or synthetic oils, e.g. esters, complex esters, hydrocarbon polymers, silicones, formals, mercaptals or polyglocol derivatives to form greases containing 5-30, and detergent or extreme pressure lubricants containing 0.5-20 weight per cent of complex; incorporated in metalworking lubricants; added to paints in proportions of 2-4 weight per cent; and to residual fuels, particularly those high in vanadium, as corrosion inhibitors.  The compositions may also include oil-soluble sulphonates equivalent to 25-80 weight per cent of the C12-C30 acid, and less than 5 per cent sulphurized sperm oil.  Cobalt complexes are of use as paint driers.  In examples: (1) greases are prepared by heating mineral oil, Hydrofol acid (hydrogenated fish oil acids), hydrogenated castor oil and hydrated lime to 130 DEG F, adding various ratios of acetic acid, heating to 500 DEG F, cooling, and homogenizing; (2) the castor oil acid is omitted; (3) mono- and di-hydroxystearic acids are also incorporated to prevent hardening, and phenyl -naphthylamine added during cooling; (6) and (7) cup greases are prepared by heating a calcium complex salt with a simple soap cup grease; (8) a grease containing equimolar amounts of Hydrofol acid and sulphonic acids as calcium salts is prepared; (9) a mixed sodium-calcium grease is obtained by mixing equal weights of the single metal complex greases; (10) a zinc-calcium grease is prepared by neutralizing the acids with zinc oxide and lime; (11) a softer grade is obtained by cutting back with more mineral oil, and the addition of titania is referred to; (12) greases are compared wherein the calcium acetate is wholly or partly preformed or prepared in situ; (13) the acetate content is part preformed strontium acetate and part calcium acetate made in situ; (14), (15) formic acid or a mixture with acetic is used; (16) lactic acid is the low molecular weight acid; (17) lead acetate is incorporated; (20) a twister ring lubricant comprises a calcium complex concentrate and petrolatum; (21) silicone fluid is thickened to a grease by mixing with acetic and Hydrofol acids and heating with lime; (22), (23) hyroxystearic acid and di-2-ethyl hexyl sebacate or di-iso-octyl azelate are also incorporated; (24) a polyester lubricating oil is used as medium for formation of the calcium complex; (25) calcium sulphonate is included in a calcium complex concentrate used as an additive for heavy duty lubricating oil; (27) a calcium complex is added to bunker fuel oil containing vanadium; (28) oxidized asphalt is blended with a calcium complex concentrate in preparing a rust preventive. Specifications 659,103, 662,650 and 680,438 are referred to.